Quantum chemical study of reactions forming a first aromatic ring in hydrocarbon flames
(2011)
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- (en) In this work, quantum chemical methods are used to determine thermodynamic properties (heats of formation, heat capacities and entropies) and rate constants for combustion modeling. Combining those methods with statistical thermodynamics and transition state theory allows the determination of data, experimentally difficult, or impossible to obtain. In the thermodynamic section of this work, the accent is put on the determination of standard heats of formation through the use of isodesmic processes. This leads to the determination of Ring Conserving Isodesmic Reactions to account for the ring strain in certain hydrocarbons, to the definition of an extrapolation procedure for the heats of formation of open-shell systems, allowing the removal of spin contamination effects, and to the proposal of an isodesmicity index, which can be used for the evaluation of the error conservation within a given bond conserving process. The kinetic part of the work starts with the determination of potential mechanisms from the analysis of energy surfaces (C6H5, C6H7 for a first aromatic ring, C10H7 and C14H9 for the further growth of Polycyclic Aromatic Hydrocarbons). From these analyses, new mechanisms are proposed, leading to new product distributions. The data concerning the formation of the first aromatic ring is introduced into a combustion kinetic model to evaluate its impact. This shows no unrealistic results, and highlights potential incompleteness in the initial mechanism, and therefore provides leads for future improvements of the combustion model.
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Lories, X. (2011). Quantum chemical study of reactions forming a first aromatic ring in hydrocarbon flames. https://hdl.handle.net/2078.5/148386